DE2525092A1 - NEW COPOLYESTERS AND METHODS FOR THEIR PRODUCTION - Google Patents

Description

PATENT LAWYERS

ζ 9 ζ Π Q 9 Dr-I ng. Wolff

H. Bartels

Dipl.-Chem. Dr. Brandes Dr.-Ing. Hero ^ Dipl.-Phys. Wolff

■ 'ι 8 Munich 22, Thierschstrasse

! Tel. (089) 293297

\ Telex 0523325 (patwo d)

Telegram address: wolffpatent, munich postal check account Stuttgart 7211 (BLZ 60010070) Deutsche Bank AG, 14/28630 (BLZ 60070070) Office hours: 8 a.m. - 12 p.m., 1 p.m. - 4.30 p.m. except saturdays

May 20, 19 25/93 Reg.No. 124

Lastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

New copolyesters and processes for their manufacture

609851 / 100S

2525032

i \ e new copolyesters and processes for their manufacture

G.

The invention relates to new copolyesters with an inherent viscosity of at least 0.4, the oxygen bonds connecting either aliphatic radicals with aromatic radicals or aromatic radicals with oxygen bonds connecting aromatic radicals are free or at least practically free. The invention also relates to a method for producing such Copolyester.

A characteristic of the copolyesters according to the invention is one high flexural strength, tensile strength and impact resistance.

In the past few decades, the use of farm bodies made from synthetic polymers has increased dramatically. In particular, be Certain synthetic polymers, including polyesters, are being used more and more in the manufacture of molded articles are subjected to heavy loads. Such synthetic polymers have mechanical properties such are that in some cases they are made from molded bodies instead of More solid materials can be used, for example instead of ceramic and metallic materials.

Although many polyester mechanical properties which are such that the polyester can be processed into valuable moldings, has nevertheless been found that most of the polyester is not -to manufacture are such shaped bodies which have dio high strength properties, as the mechanical properties of most Polyesters are not particularly high. Typical polyesters of this type are known, for example, from LS-PS 3,288,755, 5,778,410 and 3,804,805 as well as LA-PS S88,788 they are reinforced with certain reinforcing agents, such as glass fibers.

509851/1005

It was the job of the Lrfindun to produce copolyesters that were made by , .have such advantageous mechanical properties, because they can be used to produce mold bodies, u can be exposed to strong dips without losing stool consists of reinforcing these copolyesters by means of reinforcing agents.

• Yemenstuna of the invention are copolyesters with an inherent viscosity of at least 0.4, those of either aliphatic radicals with aromatic radicals connecting oxygen bonds or aromatic bonds Residues in the oxygen continuity connecting aromatic residues are free or at least practically free, and which are characterized by the fact that they are made up of divalent residues of the following Ioriaein are built up:

Ü 0

it ir

(A) -CR ₁ -C-

(D) - O - R ₂ - ü
mean:

a divalent alicyclic radical with 4 to 20 carbon atoms, a divalent aliphatic radical with 1 to 40 carbon atoms or a divalent aromatic radical with 6 to 10 carbon atoms, with the proviso that the carbonyl bonds are separated from one another by at least three carbon atoms and it also applies that at least IiO MoI-I of R-. from divalent consist of aromatic residues;

SO 98 S 1/1005 ORIGINAL INSPECTED

■ *: tr.

R _{2 is} a carbocyclic aromatic radical, with the rule that the oxygen bonds expanding the polymer chains are coaxial or parallel and opposite to one another,

that residues (C) and (D) are about 30 to about 75 UoI-I, based on make up the total moles of residues (Ii), (C) and (D);

that also the residues (D) in amounts of not more than 50 rl based on the total moles of radicals (B), (C) and (D);

that in the case of the radicals (C) the oxygen atom in meta- or is para to the carbonyl group;

and that at least 60 mol-i of the radicals (C) are ordered from the p-isomer.

According to a particularly advantageous embodiment of the invention, the radicals (C) and (D) make up about 50 to 60, .οΐ-ΐ, based on the total moles of the radicals (B), (C) and (D) and the amount of the radicals (D) Dei is about 25 to about 30 %, based on the total moles of radicals (B), (C) and (D).

According to a further, particularly advantageous embodiment of the Invention, the copolyesters are composed of the following diva- " lent residues:

(A) - C

(B) -OCH ₂ CIl ₂ O-

- ü

509851/1005

The copolyesters according to the invention can be divided into two stages Process.

Never admits the first stage of the process in the manufacture of a so-called fragmented polyester by bringing it into contact an acyloxybenzoic acid with a starting polyester an initial viscosity of at least C, 2 in the presence of a uicarboxylic acid corresponding to the radicals (A) and an aromatic one uiols corresponding to the residues (D). The starting polyester is last a polyester made from dicarboxylic acid residues and ethylene glycol residues used. As a result, the starting polyester contains recurring residues or lines from the divalent residue which, according to the Removal of the hydroxyl groups from the dicarboxylic acid remains, which is linked to the divalent test of the ethylene glycol molecule after removal the '..hydrogen f atoms are bound. When the starting polyester comes into contact these react with the acyloxyhenzoic acid by acidolysis producing the fragmented polyester.

The second stage of the process is to increase the inherent viscosity of the fragmented polyester to form the copolyester according to the invention, which consists of 4 types of uivalent radicals are constructed.

The first divalent radicals, referred to here as radicals (A), are the divalent radicals which remain after the hydroxyl groups have been removed from a dicarboxylic acid. These residues originate from the dicarboxylic acid part of the starting polyester and the dicarboxylic acid present when the starting polyester is brought into contact with the acyloxybenzoic acid. The second divalent radicals, referred to here as radicals (Ii), originate from the ethylene glycol part of the starting polyester. They are the divalent residues that remain after the removal of the hydrogen atoms from the ethylene glycol. The third diviilciitoii Xeste, here referred to as residues (C), come from outer acyloxyoenzoic acid and are the divalent residues that remain after the acyl and hydroxyl groups have been removed from the acyloxybenzoic acid. The fourth residues, referred to here as residues (D), are derived from the aromatic diol that is present when the starting

609851/1005

polyester is brought into contact with the acyloxynenzoic acid.

The starting polyester is made up of recurring residues or lines according to the following formula:

O 0 H Il

-CK ₁ -CO-CH ₀ CiI ₀ -OI LL

where R, the already given meaning aat and from the divalent Remainder exists, which after removal of the Curooxylgru ^ -en of the dicarboxylic acid that was used to produce the starting polyester remains.

Examples of dicarboxylic acids that are used to produce the starting polyester Can be used are: nalon-; üimethylmalon-; Amber-; Glutaric; Adipine-; 2-ilethyladipine-; Trimethyladipine-; Piinelin-; 2, -2-dimethylglutar-; 5,3-i) ethyl amber; Azelaic, Sebacin-; Suberine; I, S-cyclopentanedicarbon-; 1,5-cyclohexanedicarbon-; 1,4-cyclohexanedicarbon-; Terepiithal-; Isophthalic; 4-methylisophthal-; t-butyl isophthalic; 2, 5-I-iorbornaiidicarbon-; 1,4-naphthalene-; üiphen-; 4,4'-methylenedibenzoic; Diglycol; 2,5-naphthalenedicarbon ; 2, G-h'aplithalindicarbon-; 2,7-naphthalenedicarbonic; Bibenzoe-; Ataylene-bis-p-benzoic and 1,5-napiithalinedicarboxylic acids and üis (p-carboxyphenyl) methane.

If appropriate, halogenated aromatic dicarboxylic acids can also be used, for example dichloroterephthalic acid or dibromotorphthalic acid. Preferably no more than 25 moles of halogenated aromatic dicarboxylic acids are used. _{R 1} is preferably a divalent aromatic radical having 6 carbon atoms. If appropriate, the starting polyester can be produced starting from a suitable solvent instead of the dicarboxylic acid, for example starting from dimethyl terephthalate.

The mole for the production of the starting polyester consists of ethylene glycol.

509851/1005

such as Ausjang polyesters can be prepared by customary known processes produce, for example by direct 'esterification or «Jurcji a first exchange reaction and subsequent polycondensation.

Acyloxybenzoic acid, which reacted with "the starting polyester .; irU and which forms the "es to (C) des Lndcopolyes te rs in more advantageous! '.' or one of the following formulas:

O i. 0

R ₄ -CO- / 'Λ- C-CII

or

"C ¹ Il

worii. I-, a monovalent alkyl radical with 1 to 8 carbon atoms is or a monovalent aromatic radical with 6 carbon atoms and wherein at least 60 hol% of the acyloxybenzoic acid from the -Isomer exist.

In a particularly advantageous embodiment of the invention, R ₄ stands for a monovalent alkyl radical having 1 to 4 carbon atoms. According to a further, particularly advantageous embodiment of the invention, at least 90; iol- ° 6 of acyloxybenzoic acid consists of the para isomer. R 1 is preferably a monovalent alkyl radical with one carbon atom, in which case the acyloxybenzoic acid consists of p-acetoxybenzoic acid.

Examples of suitable acyloxybenzoic acids are the Eieta and para-acetoxybonzocic acids; meta- and para-propionyloxybenzoic acids; meta- and para-ijutyryloxybenzoic acids and meta- and para-ßenzoyloxyoenzoic acids.

The acyloxybenzoic acids can be prepared according to customary known processes

509851/1005

can be produced, for example by reacting a p-hydroxybenzoic acid with a carboxylic acid anhydride, for example acetic anhydride. Other known methods can also be used used for the production of acyloxy-aromatic carboxylic acids will.

The aromatic diol that provides the radicals (iJ) consists of one usual aromatic diol with a carbocyclic core and chains of expanding oxygen bonds that are coaxial or are parallel and opposite to each other.

Examples of the carbocyclic nucleus of the aromatic i) iol are divalent radicals of the following formula:

where mean:

R 'is a halogen atom or a monovalent alkyl radical having 1 to 10 carbon atoms and
η = 0, 1, 2, 3 or 4.

Furthermore, the carbocyclic nucleus of the aromatic diol can consist, for example, of a radical of the following formula:

mR ^M
where mean:

R "is a halogen atom or a monovalent alkyl radical having 1 to 10 carbon atoms and
m = 0, 1, 2, 3 or 4.

Finally, the carbocyclic nucleus of the aromatic diol

509851/1005

for example, consist of Rosten Jer the following formulas:

_4 J. _ η,? "Ι

-11 J-- pR '· «or

-pR "'

worj.κ r) odcLiten:

U " ^{1 is} a halogen atom or a monovalent alkyl radical having 1 to 10 carbon atoms and

ρ = 0, 1, 2, 3 or 4.

Preferably the carbocyclic aromatic nucleus consists of one divalent / x-s t one of the following formulas:

and

The carbocyclic aromatic is particularly advantageous Core of one of the following formula:

Examples of advantageous carbocyclic aromatic diols for The copolyesters are made up of:

509851/1005

Hydroquinone; 2-chlorohydroquinone; 2,6-i) chlorohydroquinone; 2,3,5-trifluorohydroquinone; 2, G-dibromohydroquinone; 2-ethylhydroquinone; 2-Ditert. -butylhydroquinone; 4,4'-jihydroxybiphenyl; 2-I Ic thy lily drocninoii; 1,5-naphthalenediol; 2,6-naphthalenediol and 1,4-naplithalindiol.

As already stated, the carbocyclic nucleus of the aromatic Diol, which supplies the radicals (U), have one or more halogen atoms or alkyl radicals as substituents. The substituents should not react during the polymerization and furthermore during the subsequent processing of the copolyester be thermally stable in suitable moldings. A reactivity of the substituents is undesirable, since this leads to cross-linking the copolyester can lead and the properties of the moldings, which are produced from the polyesters, in undesirable Way can affect. Advantageously, the substituents are composed of chlorine and eroin atoms and / or short-chain ones Alkyl radicals, in particular methyl, ethyl, isopropyl and n-propyl radicals. In addition to the substituents listed, a wide variety of other substituents may be present which occur during the polymerization do not react and the properties of the produced Do not adversely affect polyester, e.g. through cross-linking and steric hindrance. Such substituents are dem Known to those skilled in the art. In general, it has been found advantageous to use aromatic diols that are not more than 2, in particular have no more than one substituent. However, more than two substituents can also be present if the Substituents are comparatively small radicals, for example methyl or isopropyl radicals.

The amount of the residues (D) is not greater than 30 mol- ^? ₀ . The amount of radicals (D) is preferably from about 25 to about 301, based on the total moles of radicals (B), (C) and (D).

As previously stated, the first step in the process for making the copolyesters of the invention is to make one

509851/1005

fragmented polyester by contacting the starting polyester with an acyloxybenzoic acid in the presence of an aromatic diol and a dicarboxylic acid. The thermodynamic conditions that can be used in the first stage can be very different depending on how the process is carried out. Preferably temperatures from about 200 to about 20 ° C are used. It has often proven to be particularly advantageous to work at temperatures of about 240 to 275.degree. Temperatures below 20O ⁰ C cannot be particularly advantageous, since the reaction rate between the acyloxybenzoic acid and the starting polyester can be reduced. Although various pressures can be used, it has often proven advantageous to produce the fragmented polyester at atmospheric pressure. The reaction time for producing the fragmented polyester can vary widely. However, the starting polyester and acyloxybenzoic acid must remain in contact long enough to allow the fragmented polyester to form.

in the first stage of the process, the acyloxybenzoic acid and the starting polyester in the presence of the dicarboxylic acid and the aromatic Diols can be contacted with one another by a variety of conventional methods. In most cases they are all compounds and polymers for carrying out the process at normal temperature and normal pressure solid substances, in in which case these are mixed together and heated until they are melted. In other cases where the connections and polymers are in liquid form, they can be brought into contact with one another by simply mixing them.

As already stated, there is the second stage of the procedure of the invention for making the copolyesters in an increase in the inherent viscosity of the fragmented polyester to at least 0.4. The increase in inherent viscosity of the fragmented Polyester can be produced by one of the known customary methods according to which the molecular weight is more linear Polyester can be increased. Is the fragmented polyester

609851/1005

in melted form, the molecular weight of the fragmented polyester can be built up, for example, by a process which is similar to the polycondensation stage in the production of poly (ethylene terephthalate). In this process, the fragmented polyester is exposed to sub-atmospheric pressure and the fragmented polyester is heated while polycondensation products are withdrawn overhead. If necessary, the fragmented polyester can be agitated, for example by stirring. If the fragmented polyester is in the form of a solid mass, the molecular weight can advantageously be increased by customary known fluidization processes, such as those used, for example, to increase the molecular weight of poly (ethylene terephthalate). The thermodynamic conditions which are used during the second stage of the preparation of the copolyesters according to the invention by increasing the inherent viscosity of the fragmented polyesters can also be very different, depending on the manner in which the process is carried out. Preferably, temperatures are employed from about 230 to about 350 ⁰ C, according to a particularly advantageous embodiment of the invention, temperatures of about 260 to 29o C. At ⁰ Tejr.peraturen application of above about 35O ⁰ C can occasionally be carried out a degradation of the polymers. At temperatures below 230 ° C., the rate of increase in the inherent viscosity of the fragmented polyester can be comparatively small. It is advantageous to work at a pressure of about 800 mm to 0.05 mm of mercury.

It has proven particularly advantageous to carry out the first stage of the process of the invention at or approximately at atmospheric pressure Carry out atmospheric pressure, and the second stage of the process of the invention to start at the same pressure and gradually reduce the pressure as the inherent viscosity of the fragmented polyester is increased. The reaction time is not critical. Of course, the reaction time must sufficient to achieve the desired inherent viscosity.

According to an advantageous embodiment of the invention, the

509851/1005

Iriicront viscosity of the copolyester at least 0.5. The innorent viscosity of the copolyester can advantageously range from 0.4 to 1.0, for example 0.5, Ο, ύ or 0.7, or even across 1.0, whereby all of the uokuimte iietiioden can be used; They are common and well known for the length of the molecular weight of linear polyesters.

L'ie III rock specified inherent viscosities of the copolyesters sgeiiiäßen erfindun ^ v / ground at 25 ⁰ C using 0.50 g polymer per 100 mL of a Lösungsr.iittelgemisches of 60 volume parts and 40 Pnenol Voluiaenteilen i'etrachloräthan bestii.ii.it .

Although the first and the second stage of the process for animal division of the copolyester nacii of the invention without use a catalyst, apart from the catalyst for producing the starting polyester, can be carried out in the In the second stage of the process, a catalyst, for example a cobalt catalyst, can be used to build up the internal viscosity of the fragmented polyester.

A production according to the invention is typically carried out Copolyester based on poly (ethylene terepentalate) with an inherent viscosity of about 0.6 in granular form, terephthalic acid, Hydroquinone acetate and p-acetoxybenzoic acid. These output compounds are placed in a reaction vessel with a stirrer and heated to about 275 ° C for about an hour or up most of the acetic acid distilled from the reaction vessel and a fragmented polyester of a comparatively low melt viscosity is present. Then a vacuum is created, whereupon stirring is continued until the inherent viscosity of the copolyester prepolymer to produce a copolyester having an inherent viscosity of about 0.85.

The expression "oxygen bonds connecting aliphatic radicals with aromatic radicals" means the arrangement of atoms to adjust in the molecular chain of the polyester, if a divalent oxygen atom between an aromatic radical and a

S098S1 / 1005 ^{0 RIG! NAL! NSPECTED}

aliphatic radical is bound. As an example, be a copolyester of the prior art considered, which have been prepared from terephthalic acid, Ä'thylenenglykol and hydroxybenzoic acid is. Such a copolyester contains residues or units of the following formula:

Il

T V-C-

The copolyester is produced by hydroxy-hydroxy condensation of ethylene glycol and the hydroxy radical of Ilydroxybenzoic acid. In this case, the binding of aliphatic! to represent the aromatic residue as follows:

under "connecting aromatic radicals with aromatic radicals Oxygen bonds "is to be understood as the arrangement of atoms in the molecular chain of a polyester when there is a divalent oxygen atom connects two aromatic residues. Consider, for example, a copolyester of the prior art, produced from terephthalic acid, ethylene glycol, hydroquinone and hydroxybenzoic acid, e.g. according to US Pat. No. 3,288,755 and according to CA Pat 888 788. Such a copolyester has units of the following formula:

These units are created by hydroxy-hydroxy condensation of hydroquinone and the hydroxy radical of hydroxybenzoic acid. In this case there are bonds from aromatic radicals to aromatic ones Remainder via an oxygen atom.

509851/1005

It is characteristic of the copolyesters according to the invention that they are free or practically free of. either aliphatic residues liii with aromatic radicals connecting oxygen bonds or aromatic radicals are oxygen bonds connecting aromatic radicals. By "practically free" is to be understood, that the amount of aliphatic radicals with aromatic radicals connecting oxygen bonds or aromatic radicals with aromatic radicals connecting oxygen bonds, if such oxygen bonds exist at all, below the ability of a nuclear magnetic resonance spectrometer to be identified of the type 60 IiHz model A-60, manufactured by Varian Associates, if the copolyester lies in trifluoroacetic acid (60 MHz model A-60 Nuclear Magnetic Resonance Spectrometer). In quantitative terms, this means that the amount of aliphatic Oxygen bonds connecting residues with aromatic residues or linking aromatic residues with aromatic residues Oxygen bonds, if they exist at all, are less than about 3 mol-o. In contrast, the amount is on oxygen bonds connecting aliphatic radicals to aromatic radicals or connecting aromatic radicals to aromatic radicals Oxygen bonds in the copolyesters of the prior art Technology above the detection limit of nuclear magnetic Resonance spectrometer. In quantitative terms, this means that the amount of aliphatic radicals with aromatic radicals connecting oxygen bonds or aromatic radicals with aromatic radicals connecting oxygen bonds in the known polyesters of State of the art is above about 3 mol-I.

The copolyesters according to the invention are compared to the polyesters of the prior art, as known, for example, from US-PS 3 28S 755 and CA-PS 888 788, improved polyester, since they have improved mechanical properties compared to the known polyester, which were not to be expected.

509851/1005

Figs. 1, 2 and 3 serve to explain the invention in more detail. "* The diagrams of Figures 1, 2 and 3 illustrate important mechanical ones Properties of copolyester !! of the state of the art and according to the invention.

Fig. 1 illustrates the flexural strength or stiffness of a copolyester according to the invention and a copolyester of the prior art when the Uen ^ e of the radicals (C) of the formula:

C -

and the read of the formula (D)

within a range from 0 to 85 percent by vol, based on Total moles of residues (B), (C) and (D).

Fig. 2 corresponds to Fig. 1 except that the tensile strength is Jafc of a copolyester according to the invention is compared with the tensile strength of a copolyester of the prior art.

Fig. 3 corresponds to Figs. 1 and 2 with the exception, however, that the impact strength after impact of a copolyester according to the invention with the corresponding impact strength of a copolyester the prior art is compared.

The copolyesters of the invention corresponding to the diagrams of Figs and 3 are based, were produced according to a method as will be described in detail later, starting from of a polyester made from terephthalic acid and ethylene glycol, further terephthalic acid and various amounts of hydroquinone and p-ace toxyb enzoic acid. The inlierent viscosities of the copolyesters of the invention ranged from 0.50 to 0.68.

509851/1005

- Where -

The copolyesters of the prior Teclinik, on which FIGS. 1, 2 and 3 are based, were produced according to the customary pattern exchange process, as is described in more detail, for example, in Example 1 of US Pat. No. 3 Z'o'd 755. These copolyesters were made from diethyl tercphthalate, ethylene glycol and various amounts of ethyl p-hydroxybenzoate and hydroquinone. The inherent viscosities of the copolyesters of the prior art were from 0.63 to 0.90.

1 shows that the flexural strength (flexural synodulus) of the copolyester of the prior art is from 21090 kg / cm ² to 24UU5 kg / cm (3.0 to 3.5 10 psi), ie flexural strengths customary for polyesters of this type lie. In contrast, the flexural strengths of a copolyester according to the invention are when the radicals (C) + (jJ) are from about 30 to about 75 mol-S, based on the total moles of radicals (B), (C) and (D) and if there are no or practically no aliphatic radicals as oxygen bonds connecting aromatic radicals or aromatic radicals with aromatic radicals connecting oxygen bonds, much higher. Thus, in the case of copolyesters according to the invention, the flexural strengths are in the specified ranges

2 5

at least 49210 kg / cm (7 10 psi) while the flex strengths of the copolyesters of the prior art are less than 24605 kg / cm (3.5 10 psi). Furthermore, it can be seen that with a range from 40 to 70 Mo 1%, the flexural strengths have at least a value of 70300 kg / cm ² (10 10 ⁵ psi). In the case of 45 to 55 mol-I, the flexural strength has a value of at least 91390 kg / cm (13 10 psi). The maximum flexural strength is around 50 ϊIo 1 -%, in which case the flexural strength has a value of around 105 450 kg / cm ² (15 10 ⁵ psi).

As shown in Figure 2, the tensile strengths of the copolyesters of the prior art are about 527 to 598 kg / cm ² (7500 to 8500 psi), the tensile strength of typical polyesters of this type. In contrast, the tensile strengths are of copolyesters of the present invention, when the radicals (C) + (D) at about 30 to about 75 MOI ^0th, based on the total moles of residues (B), (C) and (D)

509851/1005

are much higher compared to the tensile strengths of the copolyesters of the prior art. Within the stated range, the tensile strengths of the copolyesters according to the invention are at least about 844 kg / cm ^ (120 opsi), while the tensile strengths of the copolyesters of the prior art are no more than 633 (90OG psi). Within a range of from about 40 to about 70 mol-a, the tensile strength in the case of a copolyester according to the invention has a value of at least about 1125 kg / cm ^ (16,000 psi). Within a range of 45 to 55 flol- ° a, the tensile strength is at least about 1968 kg / era (2000 psi). The maximum tensile strength is about 50 Iol- & and has a value on the order of about 2109 kg / cm ² (30,000 psi).

From Fig. 3 it can be seen that the impact strengths at 30 to 75 mol-I the copolyester according to the invention have unexpectedly high values when the impact strengths match the impact strengths of copolyesters of the prior art can be compared. The impact strengths are nacii within the specified range Impact in the case of the copolyesters of the invention at at least 0.1659060 mkg / 2.54 cm notch (1.2 ft.- Ib./in. Notch), whereas the impact strengths of the copolyesters of the prior art

2
be less than 0.0419686 mkg / cm (0.40 ft.- Ib./in. notch).

The impact strengths of copolyesters are 40 to 70 HoI-I according to the invention at a minimum of 0.2350335 mkg / 2.54 cm notch (1.7 ft.- Ib./in. notch). The lies within 45 to 55 iiol-1 Impact strength of a copolyester according to the invention on the order of 0.7604025 mkg / 2.54 cm notch (5.5 ft.- Ib./in. Score). The maximum impact strength of about 0.8986575 mkg / 2.54 cm notch (6.5 ft.- Ib./in. Notch) occurs at about 5μ MoI-a. Lei 50 MoI-I are also the maximum values of flexural strength and tensile strength.

The copolyesters according to the invention are suitable for the production of various moldings or pressed parts. Such moldings made from copolyesters have particularly advantageous mechanical properties

609851/1005

in which the amount of residues (C) + (D) is about 30 to about 75 Hol- !, based on the total moles of residues (B), (C) and (D) lies.

The copolyesters according to the invention are also advantageously suitable for the production of films, fibers, so-called foamed plastic products, as well as for the division of coatings as well as for production of adhesives and adhesives.

The copolyesters according to the invention can be prepared according to customary methods process known methods in conventional known devices. For example, the copolyesters according to the invention can be spun into threads by customary melt spinning processes, and then drawn, heat-set and further processed by customary known methods. Furthermore, the copolyesters according to the invention by customary known methods using customary devices, the injection molding process subject.

The copolyesters according to the invention can also be used in Process in the usual known manner after adding fillers, pigments, nucleating agents and other conventional additives. / ~

The following examples are intended to illustrate the invention in more detail.

example 1

This example illustrates the production of a typical copolyester according to the invention from terephthalic acid, ethylene glycol, 4-acetoxybenzoic acid and hydroquinone diacetate, the amount of the two divalent radicals of 4-acetoxybenzoic acid and hydroquinone being 30 mol- ⁵ », based on the total moles of these radicals plus the divalent remainder of the terephthalic acid.

In the first step of the process a fragmented poly / ^"(a nucleating agent nucleating agents, which promote the formation of amorphous polymers) was.

509851/1005

-VS-

ester prepared by placing the following components in a 5OG ml single neck round bottom flask:

38.4 g (0.2 hole) polyethylene terephthalate containing a conventional Zinc / antimony catalyst with an inherent viscosity of approximately 0.60,

27.0 grams (0.15 moles) of 4-acetoxybenzoic acid, 24.9 grams (0.15 moles) of terephthalic acid, and
29.7 grams (0.15 moles) of hydroquinone diacetate.

The flask was equipped with a stirrer and a discharge line for discharging the condensate and was placed in a thermostat with a V.'ood's metal bath at a temperature of 150 ° C. The temperature of the metal bath was increased within about 20 minutes at 27O ⁰ C. After about 5 minutes at 27O ⁰ C, the reaction started and acetic acid was removed. After about 20 minutes at 27O ⁰ C the temperature was heated to 29o ⁰ C, at which temperature was allowed to react for 30 minutes.

In the second process stage, in which the inherent viscosity of the fragmented polyester was increased, a vacuum of approximately 0.10 mm was applied for two hours and 10 minutes, where- _ in the case of polycondensation products were withdrawn overhead. Jer received Copolyester had an inherent viscosity of 0.70. the mechanical properties of the copolyester corresponded to those indicated mechanical properties of the copolyester according to the invention.

Virtually the same results were obtained when the slopes of 4-acetoxybenzoic acid and hydroquinone diacetate in uen according to the invention specified areas have been changed.

Similar results were also obtained when other aromatic diols were used in place of the hydroquinone.

509851/1005

- ac -

Example 2

i; this example illustrates the technical progress of the with lopolyesters according to the invention compared to polyesters of the state of the art with residues (Λ), (L) and (C) according to US-PS 3 77S 4IO and 5 804 b05 achieved.

In the case of the present invention, a limited class of violas is used in conjunction with ethylene glycol to make polyesters with improved mechanical properties. While from the standpoint of chemical reactivity virtually any iJiol can be used to make a copolyester, copolyesters with the advantageous properties typical of copolyesters according to the invention can only be made if a special class of diols corresponding to radicals (D) is used in conjunction with ethylene glycol . In order to show that lopolyesters made from ethylene glycol and most diols do not have the improved mechanical properties typical of copolyesters of the invention, a first group of copolyesters made from typical aliphatic diols, a second group of copolyesters made from typical cycloaliphatic diols and a third group of copolyesters made from aromatic diols (outside the scope of the invention).

The first group of copolyesters was made from polyethylene terephthalate, Terephthalic acid, 4-acetoxybenzoic acid and various aliphatic diols, the copolyester according to the in the method described in Example 1 were prepared. Each of the copolyesters produced was different from a copolyester according to the invention in that the aromatic Üiol of each copolyester has been replaced by one of the following aliphatic Diols:

Trimethylene glycol
1,3-butanediol
1,4-butanediol
1,4-butylenediol

509851/1005

1,5-pentanediol

Hexamethylene glycol

Heptamethylene glycol

1,10-uecanediol

NeopentyIgIykol

2,2,4-trimethylene-1,3-pentanediol

2,2-dimethyl-1,3-propanediol and

3-ethyl-2-isobutyl-1,3-propanediol.

While the mechanical properties of the starting from the The copolyesters produced by the specified diols were very different, the mechanical properties had in all cases the expected values, i.e. the values obtained were not better than the values of the mechanical properties of a typical Polyester, for example polyethylene terephthalate.

The second group of copolyesters was made from polyethylene terephthalate, Terephthalic acid, 4-acetoxybenzoic acid and various cycloaliphatic diols according to that given in Example 1 for the preparation of a copolyester according to the invention Procedure. The copolyesters produced differed from a copolyester according to the invention only in that the aromatic diol has been replaced by one of the following cycloaliphatic diols:

1,4-cyclohexanediol

1,2-Cyclohexanedimethano 1

1,3-cyclohexanedimethanol

1,4-Cyclohexanedii-diethanol and

2,2,4,4-tetramethyl-1,3-cyclobutanediol.

As in the case of the first group of copolyesters where aliphatic diols were used, so were the mechanical properties this copolyester is very different. However, the mechanical properties achieved corresponded to the expected properties. They were no better than the properties of a typical polyester, for example of polyethylene terephthalate.

S09851 / 1005

The third group of copolyesters was made from polyethylene terephthalate, Terephthalic acid, 4-acetoxybenzoic acid and various aromatic diols outside the range of aromatic diols according to the invention for supplying the residues (D) can be used. Following the procedure given in Example 1 for the preparation of a copolyester according to the invention were produced various copolyesters which differ from each other in that the radicals (D) are replaced by radicals of the following aromatic diols have been replaced:

bisphenol Λ

Resorcinol

o-xylenediol

m-xylenediol

4,4 · thiodiphenol

4,4'-methylenediphenol

4,4'-sulfonyldiphenol

4,4'-oxydiplienol

4,4'- (2-i \ 'orbornylidene) -diphenol and

4,4 '- (hexahydro-4,7-methanoindan-5-ylidene) diphenol

This is the case in the case of the copolyesters of the first and second groups the mechanical properties of these copolyesters were very different. In all cases, however, had mechanical properties the expected values and were no better than the mechanical properties of a typical polyester, viz Polyethylene terephthalate. Thus, if aromatic diols corresponding to the radicals (D) instead of the specified aliphatic, If cycloaliphatic and aromatic diols are used, the mechanical properties of the copolyesters obtained are according to the invention significantly improved compared to the mechanical properties of corresponding copolyesters of the prior art.

509851/1005

Claims (7)

Claims Copolyesters with an inherent viscosity of at least 0.4, derived from either aliphatic radicals with aromatic radicals Oxygen bonds or aromatic radicals with aromatic radicals connecting oxygen bonds free or at least are practically free, characterized in that they are built up from divalent radicals of the following formulas: 0 0
Il ti (A) - C - R ₁ - C - (B) -OCH ₂ CH ₂ O- (D) - 0 - R ₀ - 0 where mean: R _{1 is} a divalent alicyclic radical with 4 to 20 carbon atoms, a divalent aliphatic radical with 1 to 40 carbon atoms or a divalent aromatic radical with 6 to 16 carbon atoms, the carbonyl bonds being separated from one another by at least three carbon atoms and it also applies that at least 50 mol-i of R. consist of divalent aromatic radicals; R _{2 is} a carbocyclic aromatic radical, with the rule that the oxygen bonds expanding the polymer chains are coaxial or parallel and directed opposite one another, that the radicals (C) and (D) about 30 to about 75 MoI-I, based on make up the total moles of residues (B), (C) and (D), 509851/1005 that furthermore the residues (D) in amounts of not less than 30 Iiol-l, based on the total moles of residues (B), (C) and (D) are present, that in the case of the radicals (C) the oxygen atom is in nieta- or is para to the carbonyl group, and that at least 60 mol-I of the radicals (C) consists of the p-isomers. 2. Copolyester according to claim 1, characterized in that in the radicals (D) of the formula -0-R ₇ -O- the radical R _{9 is} a divalent radical of one of the following formula: nR ¹
in which: R ^{1 is} a monovalent alkyl radical with 1 to 10 carbon atoms or Halogen atom and
η = 0, 1, 2, 3 or 4, or
II. mR "inR" in which: R "is a monovalent alkyl radical with 1 to 10 carbon atoms or an ilalogen atom and
m = 0, 1, 2, 3 or 4, 509851/1005 2525Q92 III. in which mean: R " ^{1 is} a monovalent alkyl radical with 1 to 10 carbon atoms or Halogeriatoin and ρ = 0,1,2,3 or 4, that furthermore, 50% of the radicals (C) consist of the p-isomer and that the narrow part of radicals (C) and (D) makes up 40 to 70%. 3. Copolyester according to claim 2, characterized in that in the 'radicals (D) of the formula -0-R ₉ -O- the radical R _{0 is} a divalent radical of one of the following formulas: (TX 4. Copolyester according to one of claims 1 to 3, characterized thereby, that in the radicals (A) of the formula 0 0 R ^ is a divalent aromatic radical with 6 to 16 carbon atoms. 5. Copolyester according to claim 4, characterized gekennzeiciinet that R .. is a divalent aromatic P.est with 6 carbon atoms. 6. copolyester according to any one of claims 1 to 5, characterized in that that the residues (A), (C) and (D) consist of residues of the following "formulas: 509851/1005 originally inspected (AD C-) and CU) 7. copolyester according to claim 5, characterized in that the tests (C) and (D) 45 to 55 iiol- ^? _{Make 0 of} the cooking grates. ο. Lopolyester nacii one of claims 1 to 7, characterized in that that they are made up of remnants of the following forms: Il (C) and - ü -.v'whereby it applies that the number of residues (C) and (D) is about 45 to 55: iol-6, based on the total moles of residues (B), (C) and (D) and it also holds that the .lenge of the remainders (D) is about 25 to about 30 », based on the total moles of residues (E), (C) and (L). jjL process for the production of copolyesters according to one of claims 1 to 8, characterized in that one has a polyester with an inherent viscosity of at least 0.2 and residues of 509851/1005 Formulas (A) and (L) in the presence of an aromatic, read the Formula (JJ) supplying diol and a readable formula (A) supplying Oicaroonic acid with a hesto uer IOriiiel (C) lieicrnucn Acyloxy'beiizoesäure converts. 509851/1005 • 49. Blank page